EP2371887B1 - Matériau polymère comprenant un polymère et nanoparticule d'argent y étant dispersée - Google Patents

Matériau polymère comprenant un polymère et nanoparticule d'argent y étant dispersée Download PDF

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EP2371887B1
EP2371887B1 EP11160565.5A EP11160565A EP2371887B1 EP 2371887 B1 EP2371887 B1 EP 2371887B1 EP 11160565 A EP11160565 A EP 11160565A EP 2371887 B1 EP2371887 B1 EP 2371887B1
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Prior art keywords
polymer
silver nanoparticles
polymer material
material according
acid
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German (de)
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EP2371887A3 (fr
EP2371887A2 (fr
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Ayse Cochet
Joachim Wagner
Werner Jenninger
Daniel Rudhardt
Stefanie Eiden
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Parker Hannifin Corp
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Parker Hannifin Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof

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  • the present invention relates to a polymer material comprising a polymer and silver nanoparticles dispersed in this polymer. Such a material is particularly suitable for use as an electrode.
  • the present invention relates to a polymer material according to claim 1. Also described is a method for producing such a polymer material.
  • the invention further relates to a polymer layer composite comprising a polymer substrate and a polymer material according to the invention.
  • conductive particles such as carbon black or metal nanoparticles
  • electroconductive properties can be impart electroconductive properties as an additive to an insulator material. If the resulting material is sufficiently conductive and flexible at the same time, it can be used as a stretchable electrode in a variety of applications of electromechanical conversion, such as actuators or generators.
  • Electrode structures in high strain actuator technology by SR Ghaffarian et al., Journal of Optoelectronics and Advanced Materials 2007, 9, 3585-3591 for example, examines electrode materials based on graphite powder, carbon filled conductive grease, silver filled conductive grease and carbon filled conductive rubber.
  • the material silver is preferably used because of its high electrical conductivity and its stability to environmental conditions.
  • the production of silver nanoparticles is basically known. One way is the direct chemical reduction of dissolved metal ions in a liquid phase. The different variants of such methods differ mainly in the Reaction conditions and reaction procedures. Another possibility is the synthesis of metal oxide nanoparticles, which are reduced in a subsequent step.
  • polymeric dispersants can be added in their synthesis.
  • their presence is not always desirable when the resulting nanoparticles are to be incorporated into polymers.
  • dispersing aids reduce the electrical conductivity of the systems comprising nanoparticles, since direct contact between the nanoparticles is inevitably reduced or prevented.
  • US 2010/0040863 A1 the addition of carboxylic acids.
  • this patent application describes a process for the preparation of carboxylic acid stabilized silver nanoparticles wherein a mixture comprising a silver salt, a carboxylic acid and a tertiary amine is heated.
  • the tertiary amine is used here both as a solvent and as a reducing agent. Furthermore, this patent application states that nanoparticles with carboxylic acids having less than 12 carbon atoms are less soluble in organic solvents than those having carboxylic acids with more than 12 carbon atoms. In the process described here, however, the odor nuisance due to the use of tertiary amines is obvious in addition to the costs for the solvent.
  • a chemical reduction of metal salts to nanoparticles within a surface layer of a polymer is described in US 2009/0297829 A1 described.
  • This patent application relates to a method of introducing metal in the form of nanoparticles into the surface layer of a polymeric article and the resulting polymeric article.
  • the method comprises contacting at least a portion of the article with a solvent mixture comprising (a) water and (b) a support according to R 1 - [- O- (CH 2 ) n ] m OR 2 , where R 1 and R 2 independently of one another are linear or branched C 1-8 alkyl, benzyl, benzoyl, phenyl or H.
  • the value for n is 2 or 3 and m is 1 to 35.
  • the mixture further contains (c) a metal precursor and optionally (d) a leveling agent.
  • the contacting is performed for a period of time sufficient for at least a portion of the metal precursor to infuse into the article to obtain an article having a treated surface layer. Subsequently, the surface layer is treated with a reducing agent to obtain metal in the form of nanoparticles.
  • the WO 2005/079353 A2 discloses a nanoscale metal paste containing silver nanoparticles in matrix, for example comprising polyvinyl alcohol (PVA) or polyvinyl butyral (PVB) as binder, wherein silver nitrate is reduced by sodium citrate and iron sulfate to produce the silver nanoparticles.
  • the metal paste comprises dispersion stabilizers intended to prevent agglomeration of the silver nanoparticles.
  • dispersion stabilizers are mentioned: fatty acids, fish oils, poly (diallyldimethylammonium chloride), polyacrylic acid and polystyrenesulfonate. Such dispersion stabilizers sterically prevent the agglomeration of silver nanoparticles.
  • these steric dispersion stabilizers have the disadvantage that they reduce in the resulting conductive coatings by the surface coverage of the silver particles direct contact of the particles to each other and thus the conductivity of the coating.
  • the invention therefore proposes a polymer material according to claim 1.
  • the weight ratio of polymer to silver nanoparticles is preferably in a range of ⁇ 20:80 to ⁇ 30:70, particularly preferably in one Range from ⁇ 40:60 to ⁇ 45:55.
  • the silver nanoparticles are obtainable by reducing a silver salt in a dispersant in the presence of a dispersion stabilizer with a different reducing agent, the dispersion stabilizer being selected from the group comprising carboxylic acids having ⁇ 1 to ⁇ 6 carbon atoms, salts of carboxylic acids having ⁇ 1 to ⁇ 6 carbon atoms, sulfates and / or phosphates.
  • the polymer material is particularly suitable for the production of polymer electrodes.
  • the surface resistance of the material in the unstretched state can be, for example,> 1 ohm / square to ⁇ 25 ohms / square or> 1.5 ohms / square to ⁇ 5 ohms / square. It can be determined by the standard ASTM D-257-07.
  • the unstretched surface resistivity may be, for example,> 0.0001 ohm cm to ⁇ 0.01 ohm cm or> 0.0002 ohm cm to ⁇ 0.0005 ohm cm. It can be determined by the standard ASTM D-257-07.
  • the specific conductivity in the unstretched state can be, for example, ⁇ 300 S / cm to ⁇ 6000 S / cm, ⁇ 2000 S / cm to ⁇ 5000 S / cm or ⁇ 3000 S / cm to ⁇ 4000 S / cm. It can be determined by the standard ASTM D-257-07.
  • polymer also prepolymers which can be reacted to increase the molecular weight with chain extenders.
  • the polymer is obtainable from a polymer dispersion.
  • nanoparticles are in particular those particles having a d 50 value of less than 200 nm, preferably less than 100 nm, particularly preferably less than 60 nm, measured by means of dynamic light scattering.
  • a ZetaPlus Zeta Potential Analyzer from Brookhaven Instrument Corporation is suitable.
  • the particles are spherical or approximately spherical.
  • Suitable silver salts as precursors of the silver nanoparticles are, for example, acetates, nitrates, acetylacetonates, benzoates, bromates, bromides, carbonates, chlorides, citrates, fluorides, iodates, iodides, lactates, nitrites, perchlorates, phosphates, sulfates, sulfides and / or trifluoroacetates.
  • a dispersion stabilizer and a reducing agent different therefrom may be present.
  • the dispersion stabilizer does not or only to an insignificant extent contribute to the reduction of the silver salts.
  • This can be achieved by using a reducing agent whose redox potential is more negative than the corresponding potential of the dispersion stabilizer and is therefore preferred for thermodynamic reasons.
  • Another approach is via kinetic inhibition by employing a reducing agent that reacts faster than the dispersion stabilizer.
  • the relative proportions of dispersion stabilizer and reducing agent as well as the chosen reaction temperature can be used to influence the thermodynamic and kinetic aspects.
  • the salts of the carboxylic acids may preferably be the alkali metal or ammonium salts, preferably the lithium, sodium, potassium or tetramethyl, tetraethyl or tetrapropylammonium salts.
  • Suitable carboxylic acids are monoalkyl, dialkyl or dialkanolamines, such as diethanolamine, in question.
  • electrostatic dispersion stabilizer (s) may be removed by known purification techniques such as diafiltration, reverse osmosis and membrane filtration.
  • the dispersion stabilizers do not stabilize the silver nanoparticles against undesirable aggregation by steric hindrance, as would be the case with polymeric dispersing aids. On the contrary, repulsive electrostatic forces act here between the nanoparticles, which counteract the attractive van der Waals forces promoting the aggregation of the particles. Because the surface of the particles is not covered with sterically acting stabilizers, the silver nanoparticles and materials produced therefrom can have a higher electrical conductivity. This will be the beginning of the WO 2005/079353 A2 overcome the disadvantages discussed.
  • the silver salt is reduced by a reducing agent other than the dispersion stabilizer selected from the group consisting of carboxylic acids having ⁇ 1 to ⁇ 6 carbon atoms, salts of carboxylic acids having> 1 to ⁇ 6 carbon atoms, sulfates and / or phosphates is.
  • a reducing agent other than the dispersion stabilizer selected from the group consisting of carboxylic acids having ⁇ 1 to ⁇ 6 carbon atoms, salts of carboxylic acids having> 1 to ⁇ 6 carbon atoms, sulfates and / or phosphates.
  • the selected dispersants for example citric acid or a citrate, thus act essentially not the reduction but the dispersion of the silver nanoparticles.
  • a further advantage of the silver nanoparticles obtained in this way is that thermal transfer to larger, also macroscopic, structures ("annealing") with correspondingly increased electrical conductivity can take place at significantly lower temperatures compared to conventionally obtained nanoparticles. So this can already run at 80 ° C compared to over 200 ° C for other nanoparticles.
  • Suitable reducing agents are, for example, thioureas, hydroxyacetone, borohydrides, hydroquinone, ascorbic acid, dithionites, hydroxymethanesulfinic acid, disulfites, formamidinesulfinic acid, sulfurous acid, hydrazine, hydroxylamine, ethylenediamine, tetramethylenediamine and / or hydroxylamine sulfates.
  • borohydrides and in particular the sodium borohydride.
  • the silver nanoparticles have a zeta potential of ⁇ -5 mV to ⁇ in the dispersion medium used for their preparation in the presence of the dispersion stabilizer used for their preparation in a pH range of ⁇ pH 2 to ⁇ pH 10 -40 mV.
  • the zeta potential is the electrical potential at the shear layer of a moving particle in a suspension.
  • the zeta potential is the potential difference between the dispersion medium and the stationary fluid layer on the dispersed particle.
  • the level of this potential basically depends on the dispersing agent surrounding the nanoparticles, in particular the ions contained in the dispersing agent, and in particular on the pH of the dispersing agent.
  • the measurement of the zeta potential is carried out by means of electrophoresis.
  • various devices known in the art such as those of the series ZetaPlus or ZetaPALS from Brookhaven Instruments Corporation are suitable.
  • the measurement of the electrophoretic mobility of particles takes place by means of electrophoretic light scattering (ELS).
  • ELS electrophoretic light scattering
  • the light scattered by the particles moving in the electric field undergoes a change in frequency due to the Doppler effect, which is used to determine the migration speed.
  • the so-called "phase analysis light scattering (PALS)" technique for example with ZetaPALS devices
  • PLS phase analysis light scattering
  • the zeta potential, measured in water, in a pH range of ⁇ pH 6 to ⁇ pH 8 is between ⁇ -25 mV and> -40 mV, more preferably between ⁇ -25 mV and> -35 mV.
  • the dispersing agent in the production of the silver nanoparticles, is selected from the group comprising water, alcohols having ⁇ 1 to ⁇ 4 carbon atoms, ethylene glycol, aldehydes having ⁇ 1 to ⁇ 4 carbon atoms and / or ketones having ⁇ 3 to ⁇ 4 carbon atoms.
  • a preferred dispersant is water.
  • Non-aqueous solvents such as acetone can be used, for example, when a polymer solution is to be mixed with the nanoparticles and the solvent is subsequently removed.
  • the dispersion stabilizer in the preparation of the silver nanoparticles, is citric acid and / or citrate.
  • citric acid melts at 153 ° C and decomposes at temperatures above 175 ° C. In this way, the dispersion stabilizer can be thermally removed from a finished product.
  • the polymer is an elastomer.
  • stretchable electrodes according to the invention can be realized, as used in electromechanical transducers, in particular those based on polymers, again preferably those based on Elastomers such as silicones, acrylics, polyurethanes, polystyrene, natural rubber, synthetic rubber, rubber, gutta-percha or latex can be used.
  • Elastomers such as silicones, acrylics, polyurethanes, polystyrene, natural rubber, synthetic rubber, rubber, gutta-percha or latex
  • the acrylic elastomer VHB 4910 from 3M can be used as the elastomer material, so that elongations of up to 300% can be withstood.
  • Electromechanical converters are made, for example US 5,977,655A known.
  • the electrodes of such transducers must be adapted to the changes in the length of the transducer, since otherwise the electrodes rupture (in particular during stretching) and / or become detached (in particular when compressed).
  • US Pat. No. 6,583,533 B2 and US Pat. No. 7,518,284 B2 This was achieved by, for example, corrugated electrodes, such as those made of silver, were applied.
  • the application of these electrodes is procedurally complex and expensive.
  • the electrodes are expensive because of the high silver consumption.
  • the polymer material according to the invention makes it possible to realize flexible and extensible electrodes which do not have these disadvantages.
  • the polymer is a polyurethane.
  • polyurethane Included herein are polyisocyanurates, allophanates and other reaction products of polyisocyanates and polyisocyanate prepolymers with polyols and / or polyamines.
  • a preferred group of polyurethanes are polyurethane cast elastomers. After mixing with the silver nanoparticles, the elastomers can be thermally cured and at the same time the nanoparticles are converted into larger units.
  • Another preferred form of the polyurethane is when it can form aqueous emulsions and coalesce to a film after drying.
  • mixtures of an aqueous polyurethane dispersion and an aqueous silver nanoparticle dispersion can be prepared, which can be applied to a substrate, for example by spraying or doctoring. After removal of the water, a polymer material according to the invention is obtained.
  • polyurethanes which can be used according to the invention are aqueous polyurethane dispersions, for example hydroxy-functional polyurethane dispersions, such as Bayhydrol U: high molecular weight polyurethane dispersions (PUD) such as Bayhydrol® UH, polyurethane-polyacrylate hybrid dispersions (PUR-PAC dispersions), such as Bayhydrol® UA, polyurethane dispersions for textile coatings, such as Impranil®, preferably anionic aliphatic polyetherurethane dispersion such as Impranil 43032, Impranil® DLH, Impranil® DLN, Impranil® DLN-SD, Impranil® DLN W 50, Impranil® DLP, Impranil® LP RSC 3040 or Impranil® LP RSC 4002, anionic, aromatic polyether polyurethane dispersion such as Impranil XP 2745 or Impranil® XP 27), where the various Imprani
  • Suitable polyisocyanate and component A) are, for example, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4 , 4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate , 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and /
  • component A) may comprise a polyisocyanate or a polyisocyanate mixture having an average NCO functionality of from 2 to 4 be exclusively aliphatic or cycloaliphatic bound isocyanate groups.
  • Polyisocyanates based on hexamethylene diisocyanate, isophorone diisocyanate or the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures of the abovementioned diisocyanates can particularly preferably be used as component A).
  • the polyisocyanate prepolymers which can be used as component B) can be obtained by reacting one or more diisocyanates with one or more hydroxy-functional, in particular polymeric, polyols, if appropriate with addition of catalysts and auxiliaries and additives.
  • components for chain extension such as, for example, with primary and / or secondary amino groups (NH 2 and / or NH-functional components) for the formation of the polyisocyanate prepolymer.
  • the polyisocyanate prepolymer as component B) may preferably be obtainable from the reaction of polymeric polyols and aliphatic diisocyanates. Preference is given here as component B) to polyisocyanate prepolymers based on polypropylene glycol as polyol and hexamethylene diisocyanate as aliphatic diisocyanate.
  • Hydroxy-functional, polymeric polyols for the conversion to the polyisocyanate prepolymer B) may, for example, also be polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, Polyurethane polycarbonate polyols and / or Polyesterpolycarbonatpolyole. These can be used to prepare the polyisocyanate prepolymer individually or in any mixtures with each other.
  • Suitable polyester polyols for the preparation of the polyisocyanate prepolymers B) may be polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6 and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters or mixtures thereof, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and hydroxypivalic acid neopentyl glycol ester being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4)
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate or mixtures thereof.
  • the mean functionality of the polyol to be esterified is ⁇ 2
  • monocarboxylic acids such as benzoic acid and hexanecarboxylic acid.
  • Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
  • Hydroxycarboxylic acids which may be co-used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid or hydroxystearic acid, or mixtures thereof.
  • Suitable lactones are caprolactone, butyrolactone or homologs or mixtures thereof. Preference is given to caprolactone.
  • hydroxyl-containing polycarbonates for example polycarbonate, preferably polycarbonate, can be used.
  • polycarbonate preferably polycarbonate
  • they can be employed with a number-average molecular weight Mn of from 400 g / mol to 8000 g / mol, preferably from 600 g / mol to 3000 g / mol.
  • carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2 Methyl 1,3-propanediol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A or lactone-modified diols of the type mentioned above or mixtures thereof.
  • the diol component preferably contains from 40 percent by weight to 100 percent by weight of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives.
  • hexanediol derivatives are based on hexanediol and may have ester or ether groups in addition to terminal OH groups.
  • Such derivatives are obtainable, for example, by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to give di- or trihexylenglycol.
  • the amount of these and other components are chosen in a known manner such that the sum Does not exceed 100 weight percent, especially 100 weight percent.
  • Hydroxyl-containing polycarbonates especially polycarbonate polyols, are preferably linearly constructed.
  • polyether polyols can be used to prepare the polyisocyanate prepolymers B).
  • polytetramethylene glycol polyethers as obtainable by polymerization of tetrahydrofuran by means of cationic ring opening are suitable.
  • suitable polyether polyols may be the addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • starter molecules examples include water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, or 1,4-butanediol or mixtures thereof.
  • Preferred components for the preparation of the polyisocyanate prepolymers B) are polypropylene glycol, polytetramethylene glycol polyethers and polycarbonate polyols or mixtures thereof, with polypropylene glycol being particularly preferred.
  • polymeric polyols having a number-average molecular weight Mn of from 400 g / mol to 8000 g / mol, preferably from 400 g / mol to 6000 g / mol and more preferably from 600 g / mol to 3000 g / mol. These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
  • short-chain polyols can also be used in the preparation of the polyisocyanate prepolymers B).
  • ester diols of the stated molecular weight range such as ⁇ -hydroxybutyl-s-hydroxy-caproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
  • monofunctional isocyanate-reactive hydroxyl-containing compounds for the preparation of the polyisocyanate prepolymers B).
  • monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol or 1-hexadecanol or mixtures thereof.
  • polyisocyanate prepolymers B it is possible to react diisocyanates with the polyols at a ratio of the isocyanate groups to hydroxyl groups (NCO / OH ratio) of 2: 1 to 20: 1, for example 8: 1.
  • NCO / OH ratio ratio of the isocyanate groups to hydroxyl groups
  • urethane and / or allophanate structures can be formed.
  • a proportion of unreacted polyisocyanates can then be separated off.
  • Thin-film distillation may be used for this purpose, for example, products having residual monomer contents having residual monomer contents of, for example, ⁇ 1 percent by weight, preferably ⁇ 0.5 percent by weight, more preferably ⁇ 0.1 percent by weight, being obtained.
  • the reaction temperature may be from 20 ° C to 120 ° C, preferably from 60 ° C to 100 ° C, amount.
  • stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
  • NH 2 and / or NH-functional components can be used in addition to the chain extension in the preparation of the polyisocyanate prepolymers B).
  • Suitable components for chain extension are organic di- or polyamines.
  • compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), OH groups for the preparation of the polyisocyanate prepolymers B).
  • primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropan, 3-amino-l-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine.
  • amines having an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monoketim of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, di
  • the polyisocyanate prepolymers or mixtures thereof used as component B) may preferably have an average NCO functionality of from 1.8 to 5, particularly preferably from 2 to 3.5 and very particularly preferably from 2 to 2.5.
  • Component C) is a compound having at least two isocyanate-reactive hydroxyl groups.
  • component C) may be a polyamine or a polyol having at least two isocyanate-reactive hydroxy groups.
  • component C it is possible to use hydroxy-functional, in particular polymeric, polyols, for example polyether polyols.
  • polyether polyols for example polyether polyols.
  • polytetramethylene glycol polyethers such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening, are suitable.
  • suitable polyether polyols may be the addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • starter molecules for example, water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, or 1,4-butanediol or mixtures thereof can be used.
  • component C) is a polymer having 2 to 4 hydroxy groups per molecule, most preferably a polypropylene glycol having 2 to 3 hydroxy groups per molecule.
  • the stated polyether polyols preferably have a polydispersity of 1.0 to 1.5 and an OH functionality of greater than 1.9, more preferably greater than or equal to 1.95.
  • Such polyether polyols can be prepared in a manner known per se by alkoxylation of suitable starter molecules, in particular using double metal cyanide catalysts (DMC catalysis). This method is for example in the patent US 5,158,922 and the publication EP 0 654 302 A1 described.
  • DMC catalysis double metal cyanide catalysts
  • the reaction mixture for the polyurethane can be obtained by mixing components A), B) and C).
  • the ratio of isocyanate-reactive hydroxy groups to free isocyanate groups is preferably from 1: 1.5 to 1.5: 1 more preferably from 1: 1.02: to 1: 0.95.
  • At least one of the components A), B) or C) has a functionality of ⁇ 2.0, preferably ⁇ 2.5, preferably ⁇ 3.0 in order to introduce branching or crosslinking into the polymer element.
  • the term "functionality" in component A) and B) refers to the average number of NCO groups per molecule and in component C) to the average number of OH groups per molecule. This branching or crosslinking effects better mechanical properties and better elastomeric properties, in particular also better elongation properties
  • the polyurethane may advantageously have good mechanical strength and high elasticity.
  • the polyurethane may have a maximum stress of ⁇ 0.2 MPa, in particular from 0.4 MPa to 50 MPa, and a maximum elongation of ⁇ 250%, in particular 350%.
  • the polyurethane may have a stress of from 0.1 MPa to 1 MPa, for example from 0.1 MPa to 0.8 MPa, in particular from 0.1 MPa to 0.3 MPa (determination according to DIN 53504).
  • the polyurethane may have a modulus of elasticity at an elongation of 100% from 0.1 MPa to 10 MPa, for example from 0.2 MPa to 5 MPa (determination according to DIN EN 150 672 1-1).
  • the reaction mixture may additionally contain auxiliaries and additives.
  • auxiliaries and additives are crosslinkers, thickeners, cosolvents, thixotropic agents, stabilizers, antioxidants, light stabilizers, emulsifiers, surfactants, adhesives, plasticizers, water repellents, pigments, fillers and leveling agents.
  • the weight ratio of polymer to silver nanoparticles is ⁇ 10:90 to ⁇ 50:50. The ratio may also be in a range of ⁇ 20:80 to ⁇ 30:70. Without being bound to any theory, it is believed that at such levels of weight, the percolation threshold for the silver nanoparticles is significantly exceeded without using too much material must become.
  • the silver nanoparticles have a zeta potential of ⁇ -5 mV to ⁇ in the dispersion medium used for their preparation in the presence of the dispersion stabilizer used for their preparation in a pH range of ⁇ pH 2 to ⁇ pH 10 -40 mV. Details on this have already been described above.
  • the dispersion stabilizer in the preparation of the silver nanoparticles, is citric acid and / or citrate. Details on this have already been described above.
  • the polymer is an elastomer, preferably a silicone, acrylic, polyurethane, polystyrene, natural rubber, synthetic rubber, rubber, gutta-percha or latex. Details on this have already been described above.
  • the polymer and the silver nanoparticles are dispersed in a dispersing agent. Then two liquid phases can be mixed together. This gives a homogeneous distribution of the silver nanoparticles.
  • the dispersants for the polymer and for the silver nanoparticles are independently selected from the group comprising water, alcohols having ⁇ 1 to ⁇ 4 carbon atoms, ethylene glycol, aldehydes having ⁇ 1 to ⁇ 4 carbon atoms and / or ketones having ⁇ 3 to ⁇ 4 carbon atoms.
  • water is the common dispersant.
  • this further comprises the step of heating the resulting mixture comprising polymer and silver nanoparticles to a temperature of ⁇ 30 ° C to ⁇ 180 ° C.
  • This temperature is preferably ⁇ 50 ° C to ⁇ 150 ° C, and more preferably ⁇ 80 ° C to ⁇ 100 ° C.
  • the silver nanoparticles used can already be converted into larger and more electrically conductive structures.
  • a film obtained from a polymer dispersion can then be dried at the same time or a cast elastomer can be cured.
  • the polymer material according to the invention can be used in particular as a flexible and / or extensible electrode. Therefore, another object of the present invention is a stretchable and / or flexible electrode comprising a polymer material according to any one of claims 1 to 5.
  • another object of the present invention is a polymer layer composite comprising a polymer substrate and a polymer material according to one of claims 1 to 5.
  • the material of the polymer substrate is a dielectric elastomer, more preferably the polymer substrate is flexible.
  • the polymer substrate is provided on two opposite sides with the polymer material according to the invention.
  • the polymer material can be applied to the polymer substrate by means of doctoring, gravure printing, spraying, dipping, screen printing. So that the polymer material according to the invention adheres better to the polymer material, water and / or a surfactant can be added to it, for example.
  • a sintering process This can be accomplished via temperature or photonic sintering.
  • the polymer material according to the invention may at least partially contact the polymer substrate. But it is also possible that between the polymer substrate and the polymer material further layers such as adhesive layers are present.
  • Example 1 Preparation of a silver nanoparticle dispersion
  • the resulting dispersion was diluted with water for characterization at a ratio of 1: 200, and the pH with conc. NaOH solution set. Zeta potentials were determined for different pH values. Indicated are the pH and in brackets the zeta potential in mV: pH 10 (-43.9 mV); pH 8.8 (-34.2 mV); pH 7.5 (-38.3 mV); pH 6.3 (-29.1 mV); pH 4.9 (-23.3 mV); pH 2.4 (-23.7 mV)
  • Example 2 Preparation of a polymer material according to the invention and coating of a substrate
  • a polyurethane dielectric elastomer was selected as the substrate to be coated.
  • the previously obtained mixture was knife-coated onto the substrate at a wet film thickness of 75 ⁇ m.
  • the coated sample was dried for 30 minutes at 80 ° C in an oven.
  • the film thickness was determined by means of a profilometer to 1.1 microns.
  • the surface resistance of the unstretched sample was measured according to ASTM D-257-07, obtaining a value of 21 ohms / square.
  • the calculated surface resistivity relative to the measured film thickness was 0.00234 ohm cm and the specific conductivity was 428 S / cm.
  • curve 1 shows the course of the force F with increasing elongation D.
  • curve 2 shows the corresponding course of the electrical resistance R as a function of the elongation D.
  • the specific conductivity ⁇ is plotted as a function of the strain D. It should be emphasized by way of example that a specific conductivity of 1 S / cm or more is achieved up to an elongation of about 90%.
  • Example 3 Preparation of a polymer material according to the invention and coating of a substrate
  • the mixture was stirred for 1 hour at room temperature and then treated for 30 minutes in an ultrasonic bath.
  • a polyurethane dielectric elastomer was selected.
  • the previously obtained mixture was applied to the substrate three times in succession by means of a spray gun with a 0.3 mm nozzle batch at a pressure of 2 mbar. Subsequently, the coated sample was dried for 2 hours at 80 ° C in an oven. The film thickness was determined by means of a profilometer to 3 microns.
  • the surface resistance of the unstretched sample was measured according to ASTM D-257-07, with a value of 1.75 Ohm / Square was obtained.
  • the calculated surface resistivity with respect to the measured film thickness was 0.0002 ohm cm and the specific conductivity was 5714 S / cm.
  • the specific conductivity ⁇ is plotted as a function of the strain D. It should be emphasized by way of example that a specific conductivity of 1 S / cm or more is achieved up to an elongation of about 140%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Colloid Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Conductive Materials (AREA)

Claims (8)

  1. Matériau polymère pour une électrode extensible et/ou flexible, comprenant un polymère et, dans le polymère, des nanoparticules d'argent dispersées, caractérisé en ce que le polymère est un élastomère, de préférence il est un polyuréthane, silicone, acrylique, polystyrène, caoutchouc naturel, caoutchouc synthétique, caoutchouc, gutta-percha ou latex et le rapport en poids du matériau polymère par rapport aux nanoparticules d'argent se situe dans une gamme ≥ 10:90 et ≤ 50:50.
  2. Matériau polymère selon la revendication 1, caractérisé en ce que les nanoparticules d'argent sont obtenues par un procédé de réduction d'un sel d'argent dans un agent de dispersion en présence d'un stabilisant de dispersion avec un agent de réduction différent, où le stabilisant de dispersion est sélectionné parmi le groupe comprenant des acides carboxyliques avec des atomes de carbone ≥ 1 et ≤ 6, des sels d'acides carboxyliques avec des atomes de carbone ≥ 1 et ≤ 6, des sulfates et/ou des phosphates.
  3. Matériau polymère selon la revendication 1, caractérisé en ce que les nanoparticules d'argent présentent, dans l'agent de dispersion utilisé pour leur production en présence du stabilisant de dispersion utilisé pour leur production, dans une gamme de pH ≥ pH 2 et ≤ pH 10, un potentiel zêta de ≤ -5 mV à ≥ -40 mV.
  4. Matériau polymère selon l'une des revendications 1 à 3, caractérisé en ce que pour la production des nanoparticules d'argent l'agent de dispersion est sélectionné parmi le groupe comprenant de l'eau, des alcools avec des atomes de carbone ≥ 1 et ≤ 4, de l'alcool éthylénique, des aldéhydes avec des atomes de carbone ≥ 1 et ≤ 4 et/ou des cétones avec des atomes de carbone ≥ 3 et ≤ 4.
  5. Matériau polymère selon l'une des revendications 1 à 4, caractérisé en ce, que pour la production des nanoparticules d'argent, le stabilisant de dispersion est de l'acide citrique et/ou du citrate.
  6. Électrode extensible et/ou flexible, comprenant un matériau polymère selon l'une des revendications 1 à 5.
  7. Ensemble de couches polymères, comprenant un substrat polymère et un matériau polymère selon l'une des revendications 1 à 5.
  8. Utilisation d'un matériau polymère selon l'une des revendications 1 à 5 pour la production d'une électrode extensible et/ou flexible.
EP11160565.5A 2010-04-01 2011-03-31 Matériau polymère comprenant un polymère et nanoparticule d'argent y étant dispersée Not-in-force EP2371887B1 (fr)

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CL (1) CL2011000709A1 (fr)
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CN111163879B (zh) * 2017-09-25 2022-05-06 伊斯曼柯达公司 制备具有含氮碱的含银分散体的方法
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JP2011216487A (ja) 2011-10-27
AR080817A1 (es) 2012-05-09
CL2011000709A1 (es) 2012-02-17
US20110256383A1 (en) 2011-10-20
EP2371887A3 (fr) 2011-10-12
ZA201102439B (en) 2011-12-28
EP2371887A2 (fr) 2011-10-05

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